Polypropylene material as well as preparation method and application thereof

Abstract

The invention discloses a polypropylene material and a preparation method and application thereof, and the polypropylene material comprises the following raw materials by weight: 61.5 to 84.2% of polypropylene, 10 to 20% of SEBS, 5 to 15% of mica, 0.1 to 0.5% of polyol, 0.1 to 0.5% of an anti-reflection agent, 0.1 to 0.5% of a light diffusion agent, 0.3 to 1% of an antioxidant, 0.1 to 0.5% of a light stabilizer, and 0.1 to 0.5% of a lubricant. A residual catalyst in polypropylene is modified and chelated through polyhydric alcohol, the catalytic aging effect of the catalyst is avoided, high-transmittance homo-polypropylene powder without hindered phenol antioxidants is preferably used as a matrix, SEBS with low residual unsaturated double bond content is adopted for toughening, a specific antioxidant system is adopted, generation of chromogenic groups in the aging process is avoided, and the high-transmittance homo-polypropylene composite material is prepared. Therefore, the excellent aging and yellowing resistance of the light-transmitting polypropylene material is realized.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of polypropylene materials, especially to a kind of heat-aging yellowing light-transmitting polypropylene material and its preparation method and application, belong to high polymer material technical field. BACKGROUND

[0002] Polypropylene is one of the most widely used general-purpose plastics in the world, and has a wide application in the automotive field, but often takes non-light-transmitting application as the main. With the improvement of consumer's pursuit of automotive interior and exterior aesthetic effect, the demand of light-transmitting polypropylene material product gradually increases. This kind of light-transmitting polypropylene product will generate heat due to light source irradiation, and under the joint action of heat and oxygen, yellowing, light transmittance reduction and other aging phenomena are easy to occur in long-term use, which seriously affects the appearance and optical effect of product. In addition, the automotive application also requires polypropylene material to have certain rigidity and toughness.

[0003] Patent CN116496533A discloses a kind of high-weathering transparent polypropylene automotive exterior parts and its preparation method, by using random copolymer polypropylene and homopolymer polypropylene as resin matrix, adopting TPO toughening, mica powder reinforcing, adding semi-hindered phenolic, phosphite, benzofuranone compound antioxidant, hindered amine light stabilizer and ultraviolet absorbing agent compound weathering agent, and then spraying transparent polyurethane coating on the surface of the product, which improves the anti-yellowing and aging resistance of the product. However, the compatibility of PP and TPO is poor, which is easy to delaminate, resulting in poor rigidity and toughness balance of the mechanical properties, and the surface needs to be sprayed with polyurethane coating to solve the problem of aging yellowing, which increases the production process. Patent CN120025631A discloses a kind of polypropylene composition and its application, by using specific types of polypropylene resin and ethylene copolymer elastomer as base resin, and meanwhile compounding specific types of environmental resistance additives, realizing ideal light transmittance and toughness, and having long-term stability. However, the material rigidity is poor due to the lack of reinforcing technology, and the material yellowing resistance performance is not reflected. SUMMARY

[0004] The technical problem to be solved by the present application is to provide a light-transmitting polypropylene that has excellent optical and mechanical properties while improving the heat-aging yellowing resistance of the material.

[0005] To solve the above technical problems, the present application provides a kind of polypropylene material and its preparation method and application.

[0006] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] A kind of polypropylene material, comprising the following raw materials in the amount of by weight:

[0008] Polypropylene 61.5-84.2%,

[0009] SEBS 10-20%,

[0010] Mica 5-15%,

[0011] Polyol 0.1-0.5%,

[0012] Transparency agent 0.1-0.5%,

[0013] Light diffusion agent 0.1-0.5%,

[0014] Antioxidant 0.3-1%,

[0015] Light stabilizer 0.1-0.5%,

[0016] Lubricant 0.1-0.5%.

[0017] As a preferred technical solution of the present application, the polypropylene is homopolymer polypropylene, preferably powder homopolymer polypropylene (without antioxidant), preferably the homopolymer polypropylene powder has a melt index of 10-60 g / 10 min at 230℃ / 2.16 kg.

[0018] As a preferred technical solution of the present application, the SEBS is hydrogenated styrene-butadiene block copolymer, preferably the residual unsaturated bond content of SEBS is 0.02-0.1 relative to the molar ratio of the styrene segment; the unsaturated bond in the present application refers to carbon-carbon double bond, the molecular formula can be represented as -CH=CH-.

[0019] As a preferred technical solution of the present application, the mesh number of the mica is 100-500 mesh, preferably 200-400 mesh.

[0020] As a preferred technical solution of the present application, the polyol is one or more of pentaerythritol or trimethylolpropane, preferably pentaerythritol.

[0021] As a preferred technical solution of the present application, the transparency agent is a type α nucleating agent, preferably one or more of Millad 3905, Millad 3988, Millad NX8000K.

[0022] As a preferred technical solution of the present application, the light diffusion agent is silicone-based light diffusion agent and / or acrylic light diffusion agent, preferably one or more of SIC6591, MP-90, KMR-3EA.

[0023] As a preferred technical scheme of the present application, the antioxidant comprises one or more of semi-hindered phenolic antioxidant, thioester antioxidant, bisphenol mono-acrylate antioxidant, preferably at least two of semi-hindered phenolic antioxidant, thioester antioxidant, bisphenol mono-acrylate antioxidant are compounded. In a specific embodiment, the antioxidant can be selected from DEOX S80, antioxidant XH-245, antioxidant 1790, antioxidant AO-80, antioxidant 412S, antioxidant GS;

[0024] When the antioxidant is compounded, the compounding ratio can be adjusted by those skilled in the art, and the present application does not make special limitation thereto.

[0025] As a preferred technical scheme of the present application, the light stabilizer is one or more of light stabilizer 5585, light stabilizer 5589, light stabilizer 234.

[0026] As a preferred technical scheme of the present application, the lubricant is a stearate, more preferably one or more of zinc stearate, magnesium stearate, calcium stearate.

[0027] The present application also proposes a preparation method of the polypropylene material as described above, comprising the following steps:

[0028] The polypropylene, SEBS, mica, polyol, antireflection agent, light diffusing agent, antioxidant, light stabilizer, lubricant are mixed uniformly and then melt extruded and granulated to obtain the light-transmitting polypropylene material.

[0029] Preferably, the melt extrusion adopts an extruder, the main machine speed of the extruder is 300-500 rpm, and the melt extrusion temperature is 180-220 DEG C.

[0030] Preferably, the extruder is a double-screw extruder.

[0031] The present application also proposes an application of the polypropylene material as described above in the field of automobiles, including automobile interior atmosphere lamp, automobile exterior bumper, etc.

[0032] Compared with the prior art, the present application has the following beneficial effects:

[0033] By taking homopolymer polypropylene as the base, preferably powder polypropylene, which does not contain various antioxidants (such as hindered phenolic antioxidants) that may be contained in polypropylene granules, the conversion of hindered phenolic antioxidants inherently contained in polypropylene resin into chromogenic groups quinone in the long-term aging process can be avoided. In addition, by polyol modification, the residual catalyst in polypropylene is chelated, so that the catalyst does not catalyze aging in the aging process. The polyol also has a nucleating and permeability-increasing effect. In addition, SEBS and mica respectively play a toughening and reinforcing role, and have little effect on the light transmittance of polypropylene. DETAILED DESCRIPTION

[0034] The application will be further described below through specific examples. The examples described in the application are only used to illustrate the application and do not limit the scope of the application.

[0035] The sources of the raw materials in the examples and comparative examples of the application are as follows:

[0036] 150 (powder): homopolymer PP powder (without antioxidants), melt index 15 g / 10 min (230°C, 2.16 kg), Maoming Shihua;

[0037] 450 (powder): homopolymer PP powder (without antioxidants), melt index 45 g / 10 min (230°C, 2.16 kg), Maoming Shihua;

[0038] V30G: homopolymer PP granules (containing antioxidants), melt index 18 g / 10 min (230°C, 2.16 kg), Continental Petrochemical;

[0039] 7126: hydrogenated styrene-butadiene block copolymer, molar ratio of unsaturated bond to styrene is 0.02, Tai Xiang;

[0040] G1643: hydrogenated styrene-butadiene block copolymer, molar ratio of unsaturated bond to styrene is 0.08, Korteng;

[0041] 7311F: hydrogenated styrene-butadiene block copolymer, molar ratio of unsaturated bond to styrene is 0.3, Kolon;

[0042] HC400: 400 mesh, mica, Huajing;

[0043] 2-503: 325 mesh, mica, Xifa;

[0044] Pentaerythritol: Hubei Yihua;

[0045] Trimethylolpropane: Jilin Petrochemical;

[0046] Millad 3988: Translucency agent, M&K, USA;

[0047] Millad NX8000K: Translucency agent, M&K, USA;

[0048] MP-90: Light diffusing agent, Nippon Shokubai, Japan;

[0049] SIC6591: Light diffusing agent, Silok, Italy;

[0050] DEOX S80: Primary antioxidant of semi-hindered phenolic, Qitai Chemical;

[0051] 1010: Primary antioxidant of hindered phenolic, Tianjin Li'an Long;

[0052] 412S: Secondary antioxidant of thioester, Tianjin Li'an Long;

[0053] 168: Secondary antioxidant of phosphite, Tianjin Li'an Long;

[0054] GS: Antioxidant of bisphenol monoacrylate, free radical scavenger, Sumitomo Chemical;

[0055] 5585: Light stabilizer, Newsciences;

[0056] Zinc stearate (ZnSt): Lubricant, Fubai;

[0057] Other raw materials and reagents were purchased from commercial sources unless otherwise specified.

[0058] The main equipment used in the following examples of the present application is as follows:

[0059] Twin-screw extruder: Kobe Long (Nanjing) Machinery Co., Ltd., Model CTE35 PLUS.

[0060] Injection molding machine: Haitian Plastic Machinery Group Co., Ltd., Model MA600IIS / 130.

[0061] The main performance test methods involved in the following examples of the present application are as follows:

[0062] (1) Optical performance test: Test the light transmittance and haze according to ASTM D1003-2013, and the test equipment is colorimeter X-rite.

[0063] (2) Mechanical property test: Test the tensile property according to ISO 527-1-2019, test the bending property according to ISO 178-2010, and test the impact property according to ISO 180-2023, wherein the tensile property and bending property are tested by Instron tensile tester INSTRON5966, and the impact property is tested by impact tester INSTRON CEAST9050.

[0064] (3) Heat aging performance test: according to ISO4577-2019, the light transmittance and color of the sample after aging were tested under the condition of 120℃, 1000h heat aging.

[0065] Examples

[0066] The polypropylene materials of the examples and the comparative examples were prepared according to the ratio composition shown in Table 1 (the amount of each component in the table represents weight parts), and the preparation process included:

[0067] The polypropylene powder, SEBS, mica, polyol, antireflection agent, light diffuser, antioxidant, light stabilizer, and lubricant were mixed uniformly, then added to the extruder for melt extrusion, and granulated to obtain the polypropylene material.

[0068] The parameter settings of the twin-screw extruder were as follows: zone 1 temperature 180℃, zone 2 temperature 200℃, zone 3 temperature 220℃, zone 4 temperature 220℃, zone 5 temperature 220℃, zone 6 temperature 220℃, zone 7 temperature 220℃, zone 8 temperature 220℃, zone 9 temperature 210℃, zone 10 temperature 210℃, zone 11 temperature 200℃, zone 12 temperature 200℃, die zone temperature 200℃, feeding speed 30kg / h, and main machine speed 400rpm.

[0069] Table 1, Formulation of Examples 1-4 and Comparative Examples 1-4

[0070]

[0071]

[0072] The materials prepared in Examples 1-4 and Comparative Examples 1-4 were injection molded at 210℃. The properties of each material were tested, and the results are shown in Table 2:

[0073] Table 2, Performance test results

[0074]

[0075] From the above table, it can be seen from the comparison of Example 1 and Comparative Example 1 that using polypropylene powder without hindered phenolic antioxidant as the matrix can avoid the conversion of hindered phenolic antioxidant in the resin itself into a chromogenic group quinone during long-term aging, thereby avoiding the influence on thermal aging yellowing. From the comparison of Example 2 and Comparative Example 2, it can be seen that using SEBS with low residual unsaturated double bond content as a toughening agent is beneficial to reduce the color difference after thermal aging and improve thermal aging yellowing. From the comparison of Example 3 and Comparative Example 3, it can be seen that after modification and chelation of the residual catalyst in polypropylene using a polyol, the catalytic aging effect can be eliminated, the thermal aging performance can be improved, and nucleation and permeability enhancement can be achieved. From the comparison of Example 4 and Comparative Example 4, it can be seen that the antioxidant system of the present application can reduce the generation of quinone and other chromogenic groups, and at the same time capture free radicals in time to optimize thermal aging yellowing. In summary, by polyol modification, using homopolymer polypropylene powder without hindered phenolic antioxidant as the matrix, and using SEBS with low residual unsaturated double bond content as a toughening agent and a specific antioxidant system, more excellent anti-aging yellowing performance can be achieved.

[0076] The above description is only the preferred embodiments of the present application, and it should be pointed out that for ordinary skilled in the art, without departing from the method of the present application, several improvements and supplements can also be made, and these improvements and supplements should also be considered as the protection scope of the present application.

Claims

1. A polypropylene material, characterized in that, By weight, the following raw materials are included: Polypropylene 61.5-84.2%, SEBS 10-20%, Mica 5-15%, Polyols 0.1-0.5%, Brightening agent 0.1-0.5%, Light diffusing agent 0.1-0.5%, Antioxidant 0.3-1%, Light stabilizer 0.1-0.5%, Lubricant 0.1-0.5%.

2. The polypropylene material according to claim 1, characterized in that, The polypropylene is homopolymer polypropylene, preferably powdered polypropylene, and more preferably homopolymer polypropylene powder with a melt index of 10-60 g / 10 min at 230℃ / 2.16 kg.

3. The polypropylene material according to claim 1, characterized in that, The SEBS is a hydrogenated styrene-butadiene block copolymer, and the molar ratio of the residual unsaturated bond content in the SEBS to the styrene segment is 0.02-0.

1.

4. The polypropylene material according to claim 1, characterized in that, The polyol is one or more of pentaerythritol or trimethylolpropane, preferably pentaerythritol.

5. The polypropylene material according to claim 1, characterized in that, The antioxidants include one or more of the following: semi-hindered phenolic antioxidants, thioester antioxidants, and bisphenol monoacrylate antioxidants.

6. The polypropylene material according to any one of claims 1-5, characterized in that, The mica has a mesh size of 100-500 mesh, preferably 200-400 mesh; And / or: the penetration enhancer is an α-type nucleating agent, preferably one or more of Millad 3905, Millad 3988, and Millad NX8000K; And / or: the light diffusing agent is an organosilicon light diffusing agent and / or an acrylic light diffusing agent, preferably one or more of SIC6591, MP-90, and KMR-3EA; And / or: the light stabilizer is one or more of light stabilizer 5585, light stabilizer 5589, and light stabilizer 234; And / or: the lubricant is a stearate, preferably one or more of zinc stearate, magnesium stearate, and calcium stearate.

7. A method for preparing a polypropylene material according to any one of claims 1-6, characterized in that, Includes the following steps: Polypropylene, SEBS, mica, polyol, clearing agent, light diffusing agent, antioxidant, light stabilizer, and lubricant are mixed, melt-extruded, and granulated to obtain polypropylene material.

8. The preparation method according to claim 7, characterized in that, The extrusion is performed using a twin-screw extruder with a main extruder speed of 300-500 rpm and a melt extrusion temperature of 180-220℃.

9. An application of the polypropylene material as described in any one of claims 1-6 in the automotive field, including automotive interior ambient lighting and automotive exterior bumpers.

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